CA2435364C - Fungicide mixtures - Google Patents
Fungicide mixtures Download PDFInfo
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- CA2435364C CA2435364C CA2435364A CA2435364A CA2435364C CA 2435364 C CA2435364 C CA 2435364C CA 2435364 A CA2435364 A CA 2435364A CA 2435364 A CA2435364 A CA 2435364A CA 2435364 C CA2435364 C CA 2435364C
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/12—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring
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- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
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Abstract
The invention relates to fungicide mixtures containing, in a synergistically effective quantity, A) imidazole derivatives of formula (I) wherein R1 and R2 represent halogen and phenyl which can be substituted by halogen or alkyl, or R1 and R2, together with the bridging C=C double bond, form a 3,4-difluoromethylene dioxyphenyl group, R3 represents cyano or halogen, and R4 represents dialkylamino or isoxazol-4-yl which can carry two alkyl radicals; and B) valinamides of formula (II) wherein R' represents phenyl which is substituted in position 4 by halogen, C1-C4 alkyl or C1-C4 alkoxy, 1- or 2-naphthyl, or benzothiazol-2-yl which is substituted in position 6 by halogen, and R'' represents C3-C4 alkyl. The invention also relates to a method for controlling pathogenic fungi using mixtures of compounds (I) and (II), and the use of compounds (I) and (II) for producing such mixtures.
Description
FUNGICIDE MIXTURES
The present invention as broadly disclosed relates to fungicidal mixtures, comprising:
A) imidazole derivatives of the formula I
N
~R3 RZ N
SOZ-R' in which R1 and R2 are halogen or phenyl, which may be substituted by halogen or C1-C4-alkyl, or R1 and R2 together with the bridging C=C dbuble bond form a 3,4-difluoromethylenedioxyphenyl group;
R3 is cyano or halogen, and R4 is di(C1-C4-alkyl)amino or isoxazol-4-yl, which may carry two C1-C4-alkyl radicals;
and B) valinamides of the formula II, Ri 0, Rn y II
O
in which R' is phenyl, which is substituted in the 4-position by halogen or C1-C4-alkyl or C1-C4-alkoxy, is 1- or 2-naphthyl, or is benzothiazol-2-yl, which is substituted in the 6-position by halogen; and R" is C3-C4-alkyl;
in a synergistically effective amount.
Moreover, the invention relates to methods for controlling harmful fungi using mixtures of the compounds I and II and to the use of the compounds I and the compounds II for preparing such mixtures.
The imidazole derivatives of the formula I, their pzeparation and their action against harmful fungi are known from the literature (EP-A 298 196, WO-A 97/06171).
The valinamides of the formula II and processes for their preparation are described in EP-A-0 398 072, EP-A-0 610 764, DE-A-43 21 897, WO-A-96/07638 and JP-A 09/323984. Moreover, they can be prepared similarly to the processes described in DE 1 95 31 814.
It is an object of the present invention to provide mixtures which have an improved activity against harmful fungi combined with a reduced total amount of active compounds applied (synergistic mixtures), with a view to reducing the application rates and improving the activity spectrum of the known compounds I and II.
We have found that this object is achieved by the mixture defined at the outset. Moreover, we have found that applying the compounds I and and the compounds II simultaneously, that is either together or separately, or applying the compounds I and the compounds II successively provides better control of harmful fungi than is possible with the individual compounds alone.
The present invention as broadly disclosed relates to fungicidal mixtures, comprising:
A) imidazole derivatives of the formula I
N
~R3 RZ N
SOZ-R' in which R1 and R2 are halogen or phenyl, which may be substituted by halogen or C1-C4-alkyl, or R1 and R2 together with the bridging C=C dbuble bond form a 3,4-difluoromethylenedioxyphenyl group;
R3 is cyano or halogen, and R4 is di(C1-C4-alkyl)amino or isoxazol-4-yl, which may carry two C1-C4-alkyl radicals;
and B) valinamides of the formula II, Ri 0, Rn y II
O
in which R' is phenyl, which is substituted in the 4-position by halogen or C1-C4-alkyl or C1-C4-alkoxy, is 1- or 2-naphthyl, or is benzothiazol-2-yl, which is substituted in the 6-position by halogen; and R" is C3-C4-alkyl;
in a synergistically effective amount.
Moreover, the invention relates to methods for controlling harmful fungi using mixtures of the compounds I and II and to the use of the compounds I and the compounds II for preparing such mixtures.
The imidazole derivatives of the formula I, their pzeparation and their action against harmful fungi are known from the literature (EP-A 298 196, WO-A 97/06171).
The valinamides of the formula II and processes for their preparation are described in EP-A-0 398 072, EP-A-0 610 764, DE-A-43 21 897, WO-A-96/07638 and JP-A 09/323984. Moreover, they can be prepared similarly to the processes described in DE 1 95 31 814.
It is an object of the present invention to provide mixtures which have an improved activity against harmful fungi combined with a reduced total amount of active compounds applied (synergistic mixtures), with a view to reducing the application rates and improving the activity spectrum of the known compounds I and II.
We have found that this object is achieved by the mixture defined at the outset. Moreover, we have found that applying the compounds I and and the compounds II simultaneously, that is either together or separately, or applying the compounds I and the compounds II successively provides better control of harmful fungi than is possible with the individual compounds alone.
The formula I represents in particular imidazole derivatives of the formula I in which R1 is halogen, in particular chlorine, and R2 is tolyl, in particular p-tolyl.
Likewise, preference is given to compounds of the formula I in which R4 is dimethylainino.
More particular preference is given to the compound of the formula Ia (common name: cyazofamid), which is the one specifically recited in the claims. This compound is know from EP-A 298 196.
N
\>--CN
N CH3 Ia 0=S-N
Furthermore, preference is given to compounds of the formula I in which.P.l and R2 together with the bridging C=C double bond form a 3,4-difluoromethylenedioxyphenyl group.
In addition, preference is given to compounds of the formula I in which R4 is 3,5-dimethylisoxazol-4-yl.
Particular preference is given to the compounds of the formula lb in which X is halogen.
O
;OZx>XCH
0=S 0 lb 3a Halogen denotes fluorine, chlorine, bromine and iodine.
Particular preference is given to compounds of the formula lb in which X is bromine or chlorine.
Preference is given to compounds of the formula II' which are S-configured in the amino acid moiety. These compounds correspond to the formula II':
H H
N0`1 R' `~ /' ~7 R" II ~
l0l According to a further preferred embodiment, compounds of the formula II' are used where the carbon adjacent to the group R' is R-configured. These compounds correspond to the formula II":
~ N O, RI y RM II,.
O
The formulae II' and II" represent in particular valinamides of the formulae IIa and IIb in which the substituents in each case correspond to one row of the table below:
Likewise, preference is given to compounds of the formula I in which R4 is dimethylainino.
More particular preference is given to the compound of the formula Ia (common name: cyazofamid), which is the one specifically recited in the claims. This compound is know from EP-A 298 196.
N
\>--CN
N CH3 Ia 0=S-N
Furthermore, preference is given to compounds of the formula I in which.P.l and R2 together with the bridging C=C double bond form a 3,4-difluoromethylenedioxyphenyl group.
In addition, preference is given to compounds of the formula I in which R4 is 3,5-dimethylisoxazol-4-yl.
Particular preference is given to the compounds of the formula lb in which X is halogen.
O
;OZx>XCH
0=S 0 lb 3a Halogen denotes fluorine, chlorine, bromine and iodine.
Particular preference is given to compounds of the formula lb in which X is bromine or chlorine.
Preference is given to compounds of the formula II' which are S-configured in the amino acid moiety. These compounds correspond to the formula II':
H H
N0`1 R' `~ /' ~7 R" II ~
l0l According to a further preferred embodiment, compounds of the formula II' are used where the carbon adjacent to the group R' is R-configured. These compounds correspond to the formula II":
~ N O, RI y RM II,.
O
The formulae II' and II" represent in particular valinamides of the formulae IIa and IIb in which the substituents in each case correspond to one row of the table below:
I ~ H NuO, R S yO, Ra R ~ H3c CH'~I IIa R / N H3C CH~
IIb No. Formula R R"
II-1 IIa Br CH(CH3)2 11-2 IIa C1 CH(CH3)Z
11-3 IIa CH3 CH(CH3)2 11-4 IIa OCH3 CH(CH3)2 11-5 IIa Br CH(CH3)CH2CHg 11-6 IIa Cl CH(CH3)CH2CH3 11-7 IIa CH3 CH(CHg)CH2CH3 11-8 IIa OCH3 CH(CH3)CH2CH3 11-9 IIb F CH(CH3)2 II-10 IIb Cl CH(CH3)2 II-11 IIb Br CH(CH3)2 11-12 IIb F CH(CH3)CH2CH3 11-13 IIb C1 CH(CH3)CH2CH3 11-14 IIb Br CH(CH3)CH2CH3 Particular preference is given to compounds 11-3, 11-9 and to compound 11-15:
NyOIY ~ /CH3 For the compounds II-1 to 11-15, the configuration according to formula II' is preferred.
Particular preference is given to mixtures of the compounds of the formula Ia which coniprise as second component 11-3 (common name: iprovalicarb), 11-9 or 11-15.
When preparing the mixtures, it is preferred to employ the pure active compounds I and II, to which further active compounds against harmful fungi or against other pests, such as insects, arachnids or nematodes, or else herbicidal or growth-regulating active compounds or fertilizers can be admixed.
, . i The mixtures of the compounds I and II, or the compounds I and II
used simultaneously, together or separately, exhibit outstanding activity against a wide range of phytopathogenic fungi, in particular from the classes of the Ascomycetes, Basidiomycetes, 5 Phycomycetes and Deuteromycetes. Some of them act systemically and can thErefore also be employed as foliar- and soil-acting fungicides.
They are especially important for controlling a large number of fungi in a variety of crop plants, such as cotton, vegetable species (e.g. cucumbers, beans, tomatoes, potatoes and cucurbits), barley, grass, oats, bananas, coffee, maize, fruit species, rice, rye, soya, grapevine, wheat, ornamentals, sugar cane, and a.variety of seeds.
They are particularly suitable for controlling the following phytopathogenic fungi: Erysiphe graminis (powdery mildew) in cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits, Podosphaera leucotricha in apples, Uncinula necator in grapevines, Puccinia species in cereals, Rhizoctonia species in cotton, rice and lawns, Ustilago species in cereals and sugar cane, Venturia inaequalis (scab) in apples, Helminthosporium species in cereals, Septoria nodorum in wheat, Botrytis cinera (gray mold) in strawberries, vegetables, ornamentals and grapevines, Cercospora arachidicola in groundnuts, Pseudocercosporella herpotrichoides in wheat and barley, Pyricularia oryzae in rice, Phytophthora infestans in potatoes and tomatoes, Plasmopara viticola in grapevines, Pseudoperonospora species in hops and cucumbers, Alternaria species in vegetables and fruit, Mycosphaerella species in bananas and Fusarium and Verticillium species.
They can furthermore be employed in the protection of materials (for example the protection of wood), for example against Paecilomyces variotii.
The compounds I and II can be applied simultaneously, that is either together or separately, or successively, the sequence, in the case of separate application, generally not having any effect on the result of the control measures.
The compounds I and II are usually employed in a weight ratio of from 20:1 to 1:20, in particular from 10:1 to 1:10, preferably from 5:1 to 1:5.
. d Depending on the kind of effect desired, the application rates of the mixtures according to the invention are, in particular in agricultural crop areas, from 0.01 to 8 kg/ha, preferably 0.1 to kg/ha, in particular 0.1 to 3.0 kg/ha.
The application rates of the compounds I are from 0.01 to 1 kg/ha, preferably 0.05 to 0.5 kg/ha, in particular 0.05 to 0.3 kg/ha.
Correspondingly, in the case of the compounds II, the application rates are from 0.01 to 1 kg/ha, preferably 0.02 to 0.5 kg/ha, in particular 0.05 to 0.3 kg/ha.
For seed treatment, the application rates of the mixture are generally from 0.001 to 250 g/kg of seed, preferably 0.01 to 100 g/kg, in particular 0.01 to 50 g/kg.
If phytopathogenic harmful fungi are to be controlled, the separate or joint application of the compounds I and II or of the mixtures of the compounds I and II is effected by spraying or dusting the seeds, the plants or the soils before or after sowing of the plants, or before or after plant emergence.
The fungicidal synergistic mixtures according to the invention or the compounds I and II can be formulated for example in the form of ready-to-spray solutions, powders and suspensions or in the form of highly concentrated aqueous, oily or other suspensions, dispersions, emulsions, oil dispersions, pastes, dusts, materials for broadcasting or granules, and applied by spraying, atomizing, dusting, broadcasting or watering. The use form depends on the intended purpose; in any case, it should ensure as fine and uniform as possible a distribution of the mixture according to the invention.
The formulations are prepared in a known manner, e.g. by adding solvents and/or carriers. The formulations are usually admixed with inert additives, such as emulsifiers or dispersants.
Suitable surfactants are the alkali metal salts, alkaline earth metal salts and ammonium salts of aromatic sulfonic acids, e.g.
ligno-, phenol-, naphthalene- and dibutylnaphthalenesulfonic acid, and of fatty acids, alkyl- and alkylarylsulfonates, alkyl sulfates, lauryl ether sulfates and fatty alcohol sulfates, and salts of sulfated hexa-, hepta- and octadecanols, or of fatty alcohol glycol ethers, condensates of sulfonated naphthalene and its derivatives with formaldehyde, condensates of naphthalene or of the naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctyl-, octyl- or nonylphenol, alkylphenol or tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol/ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethes or polyoxypropylene, lauryl alcohol polyglycol ether acetate, sorbitol esters, lignosulfite, waste liquors or methylcellulose.
Powders, materials for broadcasting and dusts can be prepared by mixing or jointly grinding the compounds i or II or the mixture of the compounds I and II with a solid carrier.
Granules (e.g. coated granules, impregnated granules or homogeneous granules) are usually prepared by binding the active compound, or active compounds, to a solid carrier.
Fillers or solid carriers are, for example, mineral earths, such as silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials and fertilizers, suc.h as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders or other solid carriers.
The formulations generally comprise from 0.1 to 95% by weight, preferably 0.5 to 90% by weight, of one of the compounds I or II
or of the mixture of the compounds I and II. The active compounds are employed in a purity of from 90% to 100%, preferably 95% to 100% (according to NMR spectrum or HPLC).
The compounds I and II, the mixtures, or the corresponding formulations, are applied by treating the harmful fungi, their habitat or the plants, seeds, soils, areas, materials or spaces to be kept free from them with a fungicidally effective amount of the mixture, or of the compounds I and II in the case of separate application.
7a Application can be effected before or after infection by the harmful fungi.
Use Example The synergistic activity of the mixtures according to the invention was demonstrated by the following experiments:
, .~
IIb No. Formula R R"
II-1 IIa Br CH(CH3)2 11-2 IIa C1 CH(CH3)Z
11-3 IIa CH3 CH(CH3)2 11-4 IIa OCH3 CH(CH3)2 11-5 IIa Br CH(CH3)CH2CHg 11-6 IIa Cl CH(CH3)CH2CH3 11-7 IIa CH3 CH(CHg)CH2CH3 11-8 IIa OCH3 CH(CH3)CH2CH3 11-9 IIb F CH(CH3)2 II-10 IIb Cl CH(CH3)2 II-11 IIb Br CH(CH3)2 11-12 IIb F CH(CH3)CH2CH3 11-13 IIb C1 CH(CH3)CH2CH3 11-14 IIb Br CH(CH3)CH2CH3 Particular preference is given to compounds 11-3, 11-9 and to compound 11-15:
NyOIY ~ /CH3 For the compounds II-1 to 11-15, the configuration according to formula II' is preferred.
Particular preference is given to mixtures of the compounds of the formula Ia which coniprise as second component 11-3 (common name: iprovalicarb), 11-9 or 11-15.
When preparing the mixtures, it is preferred to employ the pure active compounds I and II, to which further active compounds against harmful fungi or against other pests, such as insects, arachnids or nematodes, or else herbicidal or growth-regulating active compounds or fertilizers can be admixed.
, . i The mixtures of the compounds I and II, or the compounds I and II
used simultaneously, together or separately, exhibit outstanding activity against a wide range of phytopathogenic fungi, in particular from the classes of the Ascomycetes, Basidiomycetes, 5 Phycomycetes and Deuteromycetes. Some of them act systemically and can thErefore also be employed as foliar- and soil-acting fungicides.
They are especially important for controlling a large number of fungi in a variety of crop plants, such as cotton, vegetable species (e.g. cucumbers, beans, tomatoes, potatoes and cucurbits), barley, grass, oats, bananas, coffee, maize, fruit species, rice, rye, soya, grapevine, wheat, ornamentals, sugar cane, and a.variety of seeds.
They are particularly suitable for controlling the following phytopathogenic fungi: Erysiphe graminis (powdery mildew) in cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits, Podosphaera leucotricha in apples, Uncinula necator in grapevines, Puccinia species in cereals, Rhizoctonia species in cotton, rice and lawns, Ustilago species in cereals and sugar cane, Venturia inaequalis (scab) in apples, Helminthosporium species in cereals, Septoria nodorum in wheat, Botrytis cinera (gray mold) in strawberries, vegetables, ornamentals and grapevines, Cercospora arachidicola in groundnuts, Pseudocercosporella herpotrichoides in wheat and barley, Pyricularia oryzae in rice, Phytophthora infestans in potatoes and tomatoes, Plasmopara viticola in grapevines, Pseudoperonospora species in hops and cucumbers, Alternaria species in vegetables and fruit, Mycosphaerella species in bananas and Fusarium and Verticillium species.
They can furthermore be employed in the protection of materials (for example the protection of wood), for example against Paecilomyces variotii.
The compounds I and II can be applied simultaneously, that is either together or separately, or successively, the sequence, in the case of separate application, generally not having any effect on the result of the control measures.
The compounds I and II are usually employed in a weight ratio of from 20:1 to 1:20, in particular from 10:1 to 1:10, preferably from 5:1 to 1:5.
. d Depending on the kind of effect desired, the application rates of the mixtures according to the invention are, in particular in agricultural crop areas, from 0.01 to 8 kg/ha, preferably 0.1 to kg/ha, in particular 0.1 to 3.0 kg/ha.
The application rates of the compounds I are from 0.01 to 1 kg/ha, preferably 0.05 to 0.5 kg/ha, in particular 0.05 to 0.3 kg/ha.
Correspondingly, in the case of the compounds II, the application rates are from 0.01 to 1 kg/ha, preferably 0.02 to 0.5 kg/ha, in particular 0.05 to 0.3 kg/ha.
For seed treatment, the application rates of the mixture are generally from 0.001 to 250 g/kg of seed, preferably 0.01 to 100 g/kg, in particular 0.01 to 50 g/kg.
If phytopathogenic harmful fungi are to be controlled, the separate or joint application of the compounds I and II or of the mixtures of the compounds I and II is effected by spraying or dusting the seeds, the plants or the soils before or after sowing of the plants, or before or after plant emergence.
The fungicidal synergistic mixtures according to the invention or the compounds I and II can be formulated for example in the form of ready-to-spray solutions, powders and suspensions or in the form of highly concentrated aqueous, oily or other suspensions, dispersions, emulsions, oil dispersions, pastes, dusts, materials for broadcasting or granules, and applied by spraying, atomizing, dusting, broadcasting or watering. The use form depends on the intended purpose; in any case, it should ensure as fine and uniform as possible a distribution of the mixture according to the invention.
The formulations are prepared in a known manner, e.g. by adding solvents and/or carriers. The formulations are usually admixed with inert additives, such as emulsifiers or dispersants.
Suitable surfactants are the alkali metal salts, alkaline earth metal salts and ammonium salts of aromatic sulfonic acids, e.g.
ligno-, phenol-, naphthalene- and dibutylnaphthalenesulfonic acid, and of fatty acids, alkyl- and alkylarylsulfonates, alkyl sulfates, lauryl ether sulfates and fatty alcohol sulfates, and salts of sulfated hexa-, hepta- and octadecanols, or of fatty alcohol glycol ethers, condensates of sulfonated naphthalene and its derivatives with formaldehyde, condensates of naphthalene or of the naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctyl-, octyl- or nonylphenol, alkylphenol or tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol/ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethes or polyoxypropylene, lauryl alcohol polyglycol ether acetate, sorbitol esters, lignosulfite, waste liquors or methylcellulose.
Powders, materials for broadcasting and dusts can be prepared by mixing or jointly grinding the compounds i or II or the mixture of the compounds I and II with a solid carrier.
Granules (e.g. coated granules, impregnated granules or homogeneous granules) are usually prepared by binding the active compound, or active compounds, to a solid carrier.
Fillers or solid carriers are, for example, mineral earths, such as silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials and fertilizers, suc.h as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders or other solid carriers.
The formulations generally comprise from 0.1 to 95% by weight, preferably 0.5 to 90% by weight, of one of the compounds I or II
or of the mixture of the compounds I and II. The active compounds are employed in a purity of from 90% to 100%, preferably 95% to 100% (according to NMR spectrum or HPLC).
The compounds I and II, the mixtures, or the corresponding formulations, are applied by treating the harmful fungi, their habitat or the plants, seeds, soils, areas, materials or spaces to be kept free from them with a fungicidally effective amount of the mixture, or of the compounds I and II in the case of separate application.
7a Application can be effected before or after infection by the harmful fungi.
Use Example The synergistic activity of the mixtures according to the invention was demonstrated by the following experiments:
, .~
The active compounds, separately or together, were formulated as a 10% emulsion in a mixture of 63% by weight of cyclohexanone and 27% by weight of emulsifier, and diluted with water to the desired concentration.
Evaluation was carried out by determinirg the infected leaf areas in percent. These percentages were converted into efficacies. The efficacy (W) was calculated as follows using Abbot's formula:
W = (1 - a)=100/p a corresponds to the fungal infection of the treated plants in % and corresponds to the fungal infection of the untreated (control) plants in %
An efficacy of 0 means that the infection level of the treated plants corresponds to that of the untreated control plants; an efficacy of 100 means that the treated plants were not infected.
The expected efficacies of the mixtures of the active compounds were determined using Colby's formula [R.S. Colby, Weeds 20-22 (1967)] and compared with the observed efficacies.
Colby's formula: E= x + y - x=y/100 E expected efficacy, expressed in % of the untreated control, when using the mixture of the active compounds A and B at the concentrations a and b x efficacy, expressed in % of the untreated control, when using active compound A at a concentration of a y efficacy, expressed in % of the untreated control, when using active compound B at a concentration of b.
Use example: Protective activity against late blight of tomatoes caused by Phytophthora infestans Leaves of potted plants of the cultivar "Grolie Fleischtomate St.
Pierre" were sprayed to runoff point with an aqueous suspension which had been prepared from a stock solution comprising 10% of active compound, 85% of cyclohexanone and 5% of emulsifier. The next day, the leaves were infected with a cold aqueous zoospore suspension of Phytophthora infestans 'of a density of 0.25 x 106 spores/ml. The plants were then placed in a water-vapor-saturated chamber at temperatures between 180C and 200C. After 6 days, the late blight on the untreated, but infected control plants had . ~
Evaluation was carried out by determinirg the infected leaf areas in percent. These percentages were converted into efficacies. The efficacy (W) was calculated as follows using Abbot's formula:
W = (1 - a)=100/p a corresponds to the fungal infection of the treated plants in % and corresponds to the fungal infection of the untreated (control) plants in %
An efficacy of 0 means that the infection level of the treated plants corresponds to that of the untreated control plants; an efficacy of 100 means that the treated plants were not infected.
The expected efficacies of the mixtures of the active compounds were determined using Colby's formula [R.S. Colby, Weeds 20-22 (1967)] and compared with the observed efficacies.
Colby's formula: E= x + y - x=y/100 E expected efficacy, expressed in % of the untreated control, when using the mixture of the active compounds A and B at the concentrations a and b x efficacy, expressed in % of the untreated control, when using active compound A at a concentration of a y efficacy, expressed in % of the untreated control, when using active compound B at a concentration of b.
Use example: Protective activity against late blight of tomatoes caused by Phytophthora infestans Leaves of potted plants of the cultivar "Grolie Fleischtomate St.
Pierre" were sprayed to runoff point with an aqueous suspension which had been prepared from a stock solution comprising 10% of active compound, 85% of cyclohexanone and 5% of emulsifier. The next day, the leaves were infected with a cold aqueous zoospore suspension of Phytophthora infestans 'of a density of 0.25 x 106 spores/ml. The plants were then placed in a water-vapor-saturated chamber at temperatures between 180C and 200C. After 6 days, the late blight on the untreated, but infected control plants had . ~
developed to such an extent that the infection could be determined visually in $.
Table A Individual active compounds Active compound Efficacy in % of Example Active compound concentration in the untreated the spray liquor Ippm] control 1 Control (85% infection) 0 (untreated) 0.2 82 2 Ia 0.1 70 0.05 53 0.2 87 3 Ib.l 0.1 73 0.05 47 0.2 70 4 11-3 0.1 53 0.05 29 5 11-9 0.1 82 0.05 70 Table B Combinations according to the invention Active compound Example mixture Observed Calculated concentration mixing efficacy efficacy*) ratio Ia + 11-3 6 0.1 + 0.1 ppm 100 86 1 : 1 Ia + 11-3 7 0.05 + 0.05 ppm 100 66 1 : 1 Ia + 11-3 8 0.1 + 0.05 ppm 100 79 2 : 1 Ia + 11-3 9 0.2 + 0.05 ppm 100 87 4 : 1 Ia + 11-3 10 0.05 + 0.1 ppm 100 78 1 : 2 Ia + 11-3 11 0.05 + 0.2 ppm 100 86 1 : 4 Ia + 11-9 12 0.05 + 0.05 ppm 100 86 1 : 1 Or 005()/52111 CA 02435364 2003-07-21 Active compound Example mixture Observed Calculated concentration mixing efficacy efficacy*) ratio 5 Ia + II-9 13 0.1 + 0.05 ppm 100 91 2 : 1 Ia + 11-9 14 0.05 + 0.1 ppm 100 92 1 : 2 10 Ib.1 + 11-3 0.1 + 0.1 ppm 100 87 1 : 1 Ib.1 + 11-3 16 0.05 + 0.05 ppm 100 62 15 1 : 1 Ib.l + 11-3 17 0.1 + 0.05 ppm 100 81 2 : 1 Ib.1 + 11-3 18 0.2 + 0.05 ppm 100 91 4 : 1 Ib.1 + 11-3 19 0.05 + 0.1 ppm 100 75 1 : 2 Ib.1 + 11-3 20 0.05 + 0.2 ppm 100 84 1 : 4 Ib.1 + 11-9 21 0.05 + 0.05 ppm 100 84 1 : 1 Ib.1 + 11-9 22 0.1 + 0.05 ppm 100 92 2 : 1 Ib.1 + 11-9 23 0.05 + 0.1 ppm 100 91 1 : 2 Ib.1 + 11-9 24 0.05 + 0.2 ppm 100 94 1 : 4 *) calculated using Colby's formula The test results show that, for all mixing ratios, the observed efficacy is greater than the efficacy which had been calculated beforehand using Colby's formula.
Table A Individual active compounds Active compound Efficacy in % of Example Active compound concentration in the untreated the spray liquor Ippm] control 1 Control (85% infection) 0 (untreated) 0.2 82 2 Ia 0.1 70 0.05 53 0.2 87 3 Ib.l 0.1 73 0.05 47 0.2 70 4 11-3 0.1 53 0.05 29 5 11-9 0.1 82 0.05 70 Table B Combinations according to the invention Active compound Example mixture Observed Calculated concentration mixing efficacy efficacy*) ratio Ia + 11-3 6 0.1 + 0.1 ppm 100 86 1 : 1 Ia + 11-3 7 0.05 + 0.05 ppm 100 66 1 : 1 Ia + 11-3 8 0.1 + 0.05 ppm 100 79 2 : 1 Ia + 11-3 9 0.2 + 0.05 ppm 100 87 4 : 1 Ia + 11-3 10 0.05 + 0.1 ppm 100 78 1 : 2 Ia + 11-3 11 0.05 + 0.2 ppm 100 86 1 : 4 Ia + 11-9 12 0.05 + 0.05 ppm 100 86 1 : 1 Or 005()/52111 CA 02435364 2003-07-21 Active compound Example mixture Observed Calculated concentration mixing efficacy efficacy*) ratio 5 Ia + II-9 13 0.1 + 0.05 ppm 100 91 2 : 1 Ia + 11-9 14 0.05 + 0.1 ppm 100 92 1 : 2 10 Ib.1 + 11-3 0.1 + 0.1 ppm 100 87 1 : 1 Ib.1 + 11-3 16 0.05 + 0.05 ppm 100 62 15 1 : 1 Ib.l + 11-3 17 0.1 + 0.05 ppm 100 81 2 : 1 Ib.1 + 11-3 18 0.2 + 0.05 ppm 100 91 4 : 1 Ib.1 + 11-3 19 0.05 + 0.1 ppm 100 75 1 : 2 Ib.1 + 11-3 20 0.05 + 0.2 ppm 100 84 1 : 4 Ib.1 + 11-9 21 0.05 + 0.05 ppm 100 84 1 : 1 Ib.1 + 11-9 22 0.1 + 0.05 ppm 100 92 2 : 1 Ib.1 + 11-9 23 0.05 + 0.1 ppm 100 91 1 : 2 Ib.1 + 11-9 24 0.05 + 0.2 ppm 100 94 1 : 4 *) calculated using Colby's formula The test results show that, for all mixing ratios, the observed efficacy is greater than the efficacy which had been calculated beforehand using Colby's formula.
Claims (10)
1. A fungicidal mixture, comprising A) the imidazole derivative of the formula Ia and B) valinamides of the formula II, in which R' is phenyl, which is substituted in the 4-position by halogen or C1-C4-alkyl or C1-C4-alkoxy, is 1- or 2-naphthyl, or is benzothiazol-2-yl, which is substituted in the 6-position by halogen; and R" is C3-C4-alkyl;
in a synergistically effective amount.
in a synergistically effective amount.
2. A fungicidal mixture as claimed in claim 1, wherein the valinamide of the formula II is as follows:
in which R is CH3 and R" is CH(CH3)2.
in which R is CH3 and R" is CH(CH3)2.
3. A fungicidal mixture as claimed in claim 1, wherein the valinamide of the formula II is as follows:
in which R is F and R" is CH(CH3)2.
in which R is F and R" is CH(CH3)2.
4. A fungicidal mixture as claimed in any one of claims 1 to 3, wherein the weight ratio of the imidazole derivative Ia to the valinamides II is from 20:1 to 1:20.
5. A method for controlling harmful fungi, which comprises treating the harmful fungi, their habitat or the plants, seeds, soils, areas, materials or spaces to be kept free from them with an imidazole derivative of the formula Ia as set forth in claim 1 and valinamides of the formula II as set forth in claim 1, 2 or 3.
6. A method as claimed in claim 5, wherein the imidazole derivative of the formula Ia as set forth in claim 1 and valinamides of the formula II as set forth in claim 1, 2 or 3 are applied simultaneously.
7. A method as claimed in claim 5, wherein the imidazole derivative of the formula Ia as set forth in claim 1 and valinamides of the formula II as set forth in claim 1, 2 or 3 are applied successively.
8. A method as claimed in any one of claims 5 to 7, wherein the imidazole derivative of the formula Ia as set forth in claim 1 is applied in an amount of from 0.01 to 2.5 kg/ha.
9. A method as claimed in any one of claims 5 to 8, wherein the valinamides of the formula II as set forth in claim 1, 2 or 3 are applied in an amount of from 0.01 to kg/ha.
10. A fungicidal composition, which is conditioned in two parts, one part comprising an imidazole derivative of the formula Ia as set forth in claim 1 in a solid or liquid carrier and the other part comprising valinamides of the formula II
as set forth in claim 1, 2 or 3 in a solid or liquid carrier.
as set forth in claim 1, 2 or 3 in a solid or liquid carrier.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10102835 | 2001-01-22 | ||
| DE10102835.0 | 2001-01-22 | ||
| PCT/EP2002/000497 WO2002056690A1 (en) | 2001-01-22 | 2002-01-19 | Fungicide mixtures |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2435364A1 CA2435364A1 (en) | 2002-07-25 |
| CA2435364C true CA2435364C (en) | 2010-04-20 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA2435364A Expired - Fee Related CA2435364C (en) | 2001-01-22 | 2002-01-19 | Fungicide mixtures |
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| US (1) | US7449195B2 (en) |
| EP (1) | EP1355531B1 (en) |
| JP (1) | JP2004522734A (en) |
| KR (1) | KR20030066819A (en) |
| CN (1) | CN100512645C (en) |
| AT (1) | ATE313260T1 (en) |
| BG (1) | BG107980A (en) |
| BR (1) | BR0206553A (en) |
| CA (1) | CA2435364C (en) |
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| DE (1) | DE50205340D1 (en) |
| EA (1) | EA006799B1 (en) |
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| ES (1) | ES2254644T3 (en) |
| HU (1) | HUP0302728A3 (en) |
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| MX (1) | MXPA03006033A (en) |
| NZ (1) | NZ527474A (en) |
| PL (1) | PL205954B1 (en) |
| SK (1) | SK286121B6 (en) |
| UA (1) | UA74418C2 (en) |
| WO (1) | WO2002056690A1 (en) |
| ZA (1) | ZA200306514B (en) |
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| ATE385693T1 (en) * | 2004-04-21 | 2008-03-15 | Basf Ag | FUNGICIDAL MIXTURES |
| JP2008189658A (en) * | 2007-01-12 | 2008-08-21 | Nissan Chem Ind Ltd | Method of controlling plant disease |
| CN103125509A (en) * | 2013-04-06 | 2013-06-05 | 海利尔药业集团股份有限公司 | Sterilizing combination containing benthiavalicarb-isopropyl and cyazofamid |
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| CA1339133C (en) * | 1987-03-13 | 1997-07-29 | Rikuo Nasu | Imidazole compounds and biocidal composition comprising the same for controlling harmful organisms |
| US5504109A (en) | 1989-05-13 | 1996-04-02 | Bayer Aktiengesellschaft | Susbstituted amino acid amide derivatives their preparation and use |
| DE3915755A1 (en) | 1989-05-13 | 1990-11-29 | Bayer Ag | FUNGICIDAL AGENTS AND SUBSTITUTED AMINO ACID DERIVATIVES AND THE PRODUCTION THEREOF |
| DE4304172A1 (en) | 1993-02-12 | 1994-08-25 | Bayer Ag | Fungicidal active ingredient combinations |
| DE4321206A1 (en) | 1993-06-25 | 1995-01-05 | Bayer Ag | Fungicidal active ingredient combinations |
| DE4321897A1 (en) * | 1993-07-01 | 1995-01-12 | Hoechst Schering Agrevo Gmbh | Substituted amino acid derivatives, processes for their preparation, compositions comprising them, and their use |
| DE4431467A1 (en) | 1994-09-03 | 1996-03-07 | Basf Ag | Caramoylcarboxamides |
| DE19531814A1 (en) | 1995-08-30 | 1997-03-06 | Basf Ag | New isomeric N-substd. valine naphthyl-ethyl amide cpds. |
| SK15898A3 (en) | 1995-08-10 | 1998-06-03 | Bayer Ag | Halobenzimidazoles and their use as microbicides |
| TW328945B (en) | 1995-08-30 | 1998-04-01 | Basf Ag | Carbamoylcarboxamides |
| US5577976A (en) | 1995-08-31 | 1996-11-26 | General Motors Corporation | Power transmission |
| JPH09323984A (en) | 1996-06-04 | 1997-12-16 | Kumiai Chem Ind Co Ltd | Amino acid amide derivative and germicide for agriculture and horticulture |
| US20020072535A1 (en) | 1997-04-18 | 2002-06-13 | Klaus Stenzel | Fungicide active substance combinations |
| DE19716256A1 (en) | 1997-04-18 | 1998-10-22 | Bayer Ag | Fungicidal active ingredient combinations |
| US6297236B1 (en) | 1998-04-06 | 2001-10-02 | Bayer Aktiengesellschaft | Fungicide active substance combinations |
| CN1330238C (en) * | 1997-04-25 | 2007-08-08 | 石原产业株式会社 | Composition for controlling harmful bio-organisms and method therefor |
| ATE250341T1 (en) | 1998-05-04 | 2003-10-15 | Basf Ag | FUNGICIDAL MIXTURES |
| DE19904081A1 (en) | 1999-02-02 | 2000-08-03 | Bayer Ag | Fungicidal active ingredient combinations |
| JP4351789B2 (en) | 1999-07-16 | 2009-10-28 | 石原産業株式会社 | Pest control composition and pest control method |
| US6624183B2 (en) * | 1999-12-13 | 2003-09-23 | Bayer Aktiengesellschaft | Fungicidal combinations of active substances |
| DE10021412A1 (en) * | 1999-12-13 | 2001-06-21 | Bayer Ag | Fungicidal active ingredient combinations |
| JP2001181114A (en) | 1999-12-27 | 2001-07-03 | Kumiai Chem Ind Co Ltd | Agricultural and horticultural bactericide composition |
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- 2002-01-19 UA UA2003087911A patent/UA74418C2/en unknown
- 2002-01-19 EP EP02702285A patent/EP1355531B1/en not_active Expired - Lifetime
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- 2002-01-19 HU HU0302728A patent/HUP0302728A3/en unknown
- 2002-01-19 KR KR10-2003-7009459A patent/KR20030066819A/en not_active Application Discontinuation
- 2002-01-19 DE DE50205340T patent/DE50205340D1/en not_active Expired - Lifetime
- 2002-01-19 SK SK900-2003A patent/SK286121B6/en not_active IP Right Cessation
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Also Published As
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| UA74418C2 (en) | 2005-12-15 |
| CN100512645C (en) | 2009-07-15 |
| HUP0302728A3 (en) | 2005-11-28 |
| CN1525819A (en) | 2004-09-01 |
| ZA200306514B (en) | 2004-09-06 |
| DE50205340D1 (en) | 2006-01-26 |
| ES2254644T3 (en) | 2006-06-16 |
| EP1355531B1 (en) | 2005-12-21 |
| US20040053980A1 (en) | 2004-03-18 |
| PL205954B1 (en) | 2010-06-30 |
| JP2004522734A (en) | 2004-07-29 |
| IL156709A0 (en) | 2004-01-04 |
| WO2002056690A1 (en) | 2002-07-25 |
| MXPA03006033A (en) | 2003-09-10 |
| BG107980A (en) | 2004-07-30 |
| KR20030066819A (en) | 2003-08-09 |
| CZ301672B6 (en) | 2010-05-19 |
| EA200300755A1 (en) | 2003-12-25 |
| CA2435364A1 (en) | 2002-07-25 |
| HUP0302728A2 (en) | 2003-11-28 |
| BR0206553A (en) | 2004-06-22 |
| SK9002003A3 (en) | 2003-12-02 |
| US7449195B2 (en) | 2008-11-11 |
| SK286121B6 (en) | 2008-04-07 |
| PL365819A1 (en) | 2005-01-10 |
| EP1355531A1 (en) | 2003-10-29 |
| EE200300344A (en) | 2003-12-15 |
| ATE313260T1 (en) | 2006-01-15 |
| NZ527474A (en) | 2004-05-28 |
| EA006799B1 (en) | 2006-04-28 |
| CZ20031887A3 (en) | 2003-09-17 |
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